Kenneth herbert saunders



Patented June 24, 1930 uumrsn srArss PATENT OFFICE ENNETH HERBERT SAUNDERS, OF MANCHESTER, ENGLAND, ASSIGNOR TO BRITISH DYESTUFFS OORPORATION LIMITED, 01' MANCHESTER, ENGLAND AZO DYES DERIVED FROM AMINOSULPHONES 1T0 Drawing. Applicationflled August 29, 1925, Serial No. 53,404, and in Great Britain October 21, 1924.

In British Letters Patent No. 18,430 of typical nitro sulphones may be represented 1913, is described the production of sulphonchlorides of phenol-o-carboxylic acids by treating phenolcarboxylic acids, or nuclear 5 substitution derivatives of these acids, with chlorsulphonic acid at temperatures below Such sulphonchlorides are'the starting materi al for the present invention; bein utllized in the production of a new series 0 azo and poly-azo dyestufis and in certain new processes of making the same. In the steps in this manufacture I have invented certain new intermediate" compounds and devised certain preparing such intermediate processes of compounds.

Ihave found that upon reduction the sulphonchlorides of aromatic o-hydroxy-carboxylic acids are converted into sulfinic acids '20 which apparently withonc exception, have nothitherto been described, and that these fsulfinic acids upon reacting with an aromatic nitro compound having a labile halogen atom,

I 0 yield new 'nitrosulphones. I find that the best results are obtained when at least one nitro group in the halogenated nitro body is in-the ortho' position to the chlorine atom. By reacting upon the sulfinic acids derived from 39 each of the sulphonchlorides mentionedin the said Letters Patent No. 18,430 of 1913 with all the commercially obtainable chloronitro cornpounds of the benzeneand naphthalene series,

the number of newnitrosulphones which can 3.; be producedis large. The structure of some as follows:

I HOOC When the nitro group, sulphones are reduced BOaH or groups, in these there are obtained aromatic'amino sulphones which are useful in the manufacture of azo dyestuffs capable of being used in mordant dyeing without great change in shade. In these dyestufi's a chelate group is carried on one portion of the compound molecule while another portion carries the color-giving or chromop'horic groups. By chelate group I mean an orthohydroxy-carboxylic group which is characterdivisions of, the present application.

having the amino group or groups attached thereto. Such mixed sulphones may be represented by the general formula H0 1 I- r-( H wherein R represents a benzene residue, R,

represents 'a benzene or naphthalene residue.

The said residues represented by R and R may or may not be further substituted and m is 1 or 2 and in which the OH and COOH groups attached to the R are ortho to each other. By the term aryl residue, I mean benzene or naphthalene residues which may or may not befurther substituted. Mixed aromatic amino sul'phones-of this type are setforth and claimed in my copending ap lications Ser. Nos. 303,37 land 398,805whic are In preparing azo dyestufis from such mixed sulphones, any hydroxy-, amino oraminohy roxy compound capable of coupling may be used as the second component, the choice chromop OHand COOH groups attached tojthe R are being determined by the shade or properties (e. 'g. solubilit fastness to chlorine, etc.) of the required yestufi. Dis! or polyazo-dyestufis may be built up if desired. Many different-s'peoific dyestuffs may be produced in accordance with the present-invention. All of these new dyestufl's may be represented by the following generic formula H t-B 110 wherein R represents a benzene residue and R represents a benzene or naphthalene-residue having an azo grou attachedthereto, thegroufinng represente by R possessing oric properties and in which the ortho to each other. These new dyes are like- -wise mixed sulphones carrying two aryl groups (benzene) of different character, one of the aryl groups (benzene) being chromophoric and the other (benzene or naphthalene) being of non-chromophoric character but capable of uniting with mordants. Such azo dyestuffs possess the characteristic property of being capable of application in mordant dyeing without substantial change in shade. They are characterized by having the chelate group separated from and connected to the chromophoric portion of the dycstuff by a sulphone bridge; the sulphonc bridge acting as a v chromophoric screen. Hence when these new dyestuffs are fixed on animal or vegetable fibers by metallic mordants little or no change in shade occurs.

The present invention is more particularly directed to those azo dyestuffs which may be represented by the general formula wherein R represents a coupling component trate the invention further but the invention is not confined to the examples Ewample I 10 parts of salicylic sulphonchloride (prepared, for instance, according tothe method of British Letters Patent 18430 of 1913), are dissolved in20 parts of alcohol and the solu-' tion rapidly agitated with external cooling. Slightly more than one atomic proportion of zinc dust (about 2.8 to 3 parts) is then added in small'portions so that the'temperature does not rise-unduly. Soon after the addition of zinc theseparation of crystals begins and continues rapidly until finally the "content of the vessel becomes a semi-solid magma. The solvent is filtered oil, the residue is dried and dissolved in caustic soda,

preferably as a strong solution. This. solution is then filtered, chilled and slowly made acid to Congo paper during gentle agltation. Upon standing the salts formed throw out the sulfonic. acid "as small, shining crystals working under the conditions above described, the product obtained appears to con 1-10 which can be filtered off and dried. When sist of an eq'uimolecular compound of the free sulfionic acid with its acid sodium salt and is sufliciently pure for use in most processes without further purification. It decomposes slowly on standm and can be readily distinguished from t e 5-sulphonic acid whose crystals melt at since-on heating it does notdecompose until about 200 C. It is insoluble in ether and. most organic solvents, but soluble in alcohol. With ferric chloride it gives a bluish-red color in dilute aqueous solution. i

The method described above may be widely varied, for instance, the reactionmay with advantage be carried out in the presence of an acid-binding agent, such as-calcium carbonate. 'The crude zinc sulfinate may be de- III salicylic acid yield t composed with sodium carbonate solution either hot or cold, and the sulfinic acid liberated from the solution after removal of zinc carbonate.

By similar treatment, o-cresotinic sulphonchloride and the sul honchloride of 3-chloro he corresponding sulfinic acids which, form -colorless crystals. The

crude products as usually obtained melt at acid of melting point 159 C. as there described can be obtained throu h the decomposition with mineral acid 0 my zinc salt or the calcium salt.

' Example II 10 parts of salicylic sulfim'c acid, 13 parts of the sodium salt of 4-chloro-3-nitrobenzene sulphonic acid, 5.3 parts of sodium carbonate and 25 parts of water are boiled together for some hours, the solution becoming deep orange color as reaction proceeds. The sulphone which has been produced may be isolated either by acidifying the hot solution or by forming the barium salt and evaporating to crystallization whena ale yellow granular substance, readily soluble in warm water, is obtained. For the present purposes, the nitrosulphone in the solution may be reduced without isolation by any convenient method of reduction e. g., iron filingsm acid, zinc dust and acid, stannous chloride, sodium sulphide, etc., while the solution of the amine so obtained may have its content of diazotizable amino compound determined by titration with standard nitrite solution and used directly for dye-making. The solutions ofthe amine itself'are colorless when pure. The amino sulphone in the form of the free acid has the probable formula H000 NH:

- position ortho to the hydroxy group.

By using an equivalent quantity of o-cresotinic sulfinic acid and working in the same manner as above, the corresponding nitro sulphone and amino sulphone may be ob-tained.

clear at first, a

tained as compounds closely similarto those described.

Example 111 10 parts of o-cresotinic sulfinic acid are added to a boiling alcoholic solution of 9.35 parts of 2 t-dinitro-chlorobenze and 4.6 parts of potassium acetate. From the solution, co ious white precipitate soon separates and al ter boiling for some time and cooling, this is filtered oif. The nitro sulphone so obtained has in the form of the free acid the probable formula 'nooo The dinitrosulphone may be purified by dissolving in alkali and reprecipitatin with acid. t may be reduced in a variety o ways, but a convenient agent is stannous chloride which smoothly reduces either one or both of the nitro grou s. In the first instance, a diazotizable amlne is produced and in the second a diamine which gives a deep brown dyestufi by the action of nitrous acid. This diamine yields mono acidyl derivatives which are useful azo dyestufl' components.

In a similar manner, 1-chloro-2z4-dinitro naphthalene condenses with sulfinic acids while 2: 6-dinitro-chloro-benzene-4-sulphonic acid condenses either in aqueous or alcoholic solution.

Example I V An acid solution containing 10 parts of the amino sulphone prepared according to Example II is cooled .and diazotized with a solution of 2.32 parts of sodium nitrite. Part of the diazo; compound separates as a pale yellow solid. When the reaction is complete, the diazo solution is allowed to flow into an alkaline solution of 7.73 parts of betahydroxynaphthoic anilide. When coupling is complete, the dyestufi' is salted from the hot alkaline solution, filtered and dried, forminga bright scarlet powder. Printed on cotton cloth with a chrome mordant, the dyestuff yields salmon pink fshades fast to hot soap and chlorine. v Instead of beta-hydroxynaphthoic anilide,

" beta-naphthol (orange), beta -naphthyla'm-.

(scarlet), ethyl-beta-naphthylamine (bluish-red), phenyl methyl pyrazolone pure yellow), ethyl benzylaniline (orange) etc. may be used. In addition to being useful printing colors, all the above may be dyed on wool as acid chrome colors yielding shades which resist milling and potting- If the amino sulphone derived from o-cresotinic sulfinic acid and 4-chloro-3-nitrobenzene sulphonic acid be used, dyestuffs closely resemblin those mentioned above are obhe probable formulae of some of the materials prepared according to this example may be indicated as follows, the formula given in each case being that of the dye in the form of its free acid. Dye from the anilide of beta-hydroxynaphthoic acid HOOC E (fin- A Dye from pyrazolone nooc OSOu-OSOQI Dye from ethylbenzylaniline 10 parts of the disodium salt of the amino sulphone obtained by reducing the nitrosulphone produced from 5 -sulfino salicylic acid and-4-chloro-3-nitrobenzoic acid that is to say, 2-amin0-4-hydroxy-4 3-dicarboxydiphenyl sulphone are dissolved in water containing 1.82 parts of sodium nitrite. This solution is allowed to run with rapid stirring and cooling into dilute acid whereby the di-, azo derivative is formed. This latter is yellow in color and sparingly soluble in water. The diazo compound is then allowed to run in a thin stream into an acid solution of 3.78 parts of beta-naphthylamine. The solution is slowly made alkaline, warmed, filtered and the dyestufi salted out from solution and dried. Printed on cotton cloth with a chrome mordant, the dyestulf yields bright scarlet shades fast to hot soap.

Instead of beta-naphthylamine, beta-naph- Oso coon When 1 :4-naphtholsulphonic acid is employed the free acid of the dye has the following probable formula HOOO The following formula represents the compound which may be obtained when using 1 8 dihydroxynaphthalene 3 6-disulphonic acid nooc noOsm-OCoon H0 0B.

H03 SOaH Example VI parts of acetyl-J-acid, the dyestuff is salted.

out from solution, filtered off and dried. When printed on cotton it yields a heliotrope fast to warm soap. The structural formula -may be represented as follows:

E's-ample VII 10 arts of the monamine which has the proba le formula nooo N0: BOO-@rO-Nlh and which is obtained by reducing with stannous chloride the dinitrosulphone of Example III are dissolved in sodium carbonate, 1.96 parts of sodium nitrite added, and the chilled solution slowly acidified. 'The diazo compound separates in yellow flakes and the suspension is run into an alkaline solution of 7 .4 parts of the sodium salt of beta-naphthylamine-methyl-omega-sulphonate. Coupling takes place at once. The finished dyestufi is salted out from solution, filtered off and dried at a low temperature. When printed on cotton with a chrome mordant, the dyestufl yields red shades fast to hot soap. This dyestufi has the probable formula H000 No, nmomsoar HOQOHOa m v I Example VIII The diamine obtained by the reduction of the condensation product of 5-sulfino-sahcylic acid with 2: 4-dinitrochloro-benzene is boiled with excess oxalic acid until nitrous acid'no longer gives a brown dyestufi but a beta-naphthol may be indicated as follows:

o-OorQ-i-i-ooon The 5-sulphino-salicylic acid, its salts, homologues and analogues, such as can be obtained according to my invention, possess the following reactions :They give an intensely blue colored solution when mixed with phenetol and strong sulphuric aci'd, and a deep red to' purple solution with ferric chloride. Two molecules of one of the sulfinic acids will go into reaction with 1 molecule shades fast to chlorine and warm soap. The structural formula of the dye derived from of nitrous. acid, yielding a sulphydroxamic acid.

My new monoand dinitrosulphones possess the following properties :-They are white or pale yellow colored substances easily obtained in the crystalline state from aqueous or alcoholic solution. They dissolve in colored solutions and. give a 'red coloration in dilute aqueous solution with ferric chloride. If the ortho position to the bycaustic alkalies to give yellow to orange droxyl oup is not occupied they chlorinate smoot y with aqueous alkali hypochlorite. They are quantitatively reduced by titanous chloride.

The mono-amino sulphones of this invention occur as well defined colorless crystalline substances when obtained by crystallizing the alkali metal salts from water. They give a red coloration with dilute aqueous ferric chloride solution and their diazo compounds are usually of a pale yellow color sparingly soluble in water.

The diamino sulphones give a red coloration with dilute aqueous ferric chloride solution and exhibit allthe general properties of diamines of the benzene series. v

' All my new dyestuffs not containing an ox idizable second component (e. g. 1:8-dihydroxynaphthalene-3: 6-disulphonic acid) are characterized by the ,property that practically no change in shade occurs on chroming the d eings onvwool, but that after chroming the ades become fast to milling potdiphenylsulfone compound containing a hyting. Similarly when printed on cotton with.

a chrome mordant the shade of the original dye solution is preserved but the print is fast to warm soap.

What I claim is:

' 1. In the manufacture of azo dyes, the process which comprises reacting upon a 5- sulphino salicylic acid with an aromatic nitro compound having a labile chlorine atom, reducing the nitro sulphone to an amino sulphone, diazotizing said amino sulphone and then coupling the diazotized sulphone with the usual azo "dye coupling components.

2. In processes of producing azo dyestuffs the steps comprising diazotizing an aminodroxyl and a carboxyl group in ortho position to each other in the nucleus containing no amino group, in which both nuclei can be further substituted and which can be represented by the general formula H N-C H4SO2C 5 s(OI-I) (COOH) coupling the diazo compound obtained with an aromatic coupling component and isolating the azo dyestuif formed.

3. In processes of producing azo dyestuffs the steps comprising diazotizing an aminodiphenylsulfone sulfonic acid compound containing a hydroxyl and carbonyl grou in ortho position to each other in the nuc eus containing no amino group, in which both nuclei can be further substituted and which can be represented by the general formula (H N). (SO H) C H SO2"'C6 3(OH) (COOI-I) coupling the diazo compound obtained with a coupling component of the naphthalene series and isolating theazo dyestuif formed.

4. The process of manufacturing azo dyes which comprises diazotizing an amino sulph ine having the probable structural formu a wherein R represents an aromatic nucleus which may be further substituted, and coupling said diazotized amino sulphone with the usual coupling components. a

5. The process of manufacturing azo dyes which comprises diazotizing an amino sulphone having the structural formula CODE and coupling said diazotized amino supho'ne and coupling said diazotized amino sulphones with beta-naphthol.

7. Azo dyes carrying a chelate group and adapted for mordant dyeing with the chelate group separated from the chromophore group by a sulphone bridge, said azo dyes being mixed sulphones with the'probable formula adapted for mordant dyeing, with the chelate group separated from the chromophore group a sulphone bridge,- said azo dyes being mixed sulphones with the probable formula Rr-SOrRz-Y HO wherein R represents a benzene residue and R represents a benzene or naphthalene-residue and in which the said residue R and R2 may or may not be further substituted and Y represents the substituent group-N=NR' probable formula wherein R represents a benzene residue and in the form of the free acid the structural R represents a benzene or naphthalene resi-' formula due and in which the said residues R1 and R; on may or may not be further substituted, and j 5 R, represents a coupled azo dye component v 0011 and in which the COOH, and OH groups are ortho to each other, the said dyestufis producing shades which are substantially unchanged when chromed.

1o 10. Azo dyestufis carrying a chelate group and adapted for mordant dyeing with the chelate group separated from the chromo- H phore group by a sulphone bridge, the said 0m azo (1 es being mixed sulphones having the probable formula- In testimony whereof I hate hereunto af- 8o fixedm signature. 3000 HERBERT SAUNDERS.

wherein R represents a benzene or naphthalene residue, R represents hydrogen, a sulphonic group, nitro group or oxalylated amino group, R represents H, CH or Cl and 25 R represents a coupled residue from an azo dye coupling component.

11. As new products, the azo dyes prepared by diazotizing and coupling an amino sulphone having the structural formula. 3 noo o no-O-so m-Nm wherein R represents an aromatic nucleus H 35 which may or may not be further substituted,

with the usual azo dye coupling component. I

12. As new products mordant azo dyestuffs of the general formula R,-N= u-dm sof-ceHa (000E) in which the coupling component R is a naphthalene derivative and the hydroxyl and carboxyl groups are in ortho position to each 45 other and in which the benzene nuclei of the diphenylsulfone can be further substituted, said dyestufis in the form of their alkali metal salts being easily soluble in water and concentrated suliuric acid and said dyestufi's dyeil'lg textile fibres, particularly on chrome mor a V p dants, in exceedingly fast shades. V 13. As new products mordant azo dyestufi of the general formula 5 .ooon N=NB,

no OnH .in which R, is a coupling component, said salts being easily soluble in water and con centrated sulfuric acid and said dyestufis dyeing animal fibres, particularly on chrome mordants,-in exceedingly fast shades. V c5 14. As a new product, the azo dye having dyestufis in the form of their alkali metal Certificate of Correction.

Patent No. 1,766,946.

I KENNETH HERBERT SAUNDERS i Granted June.2 4, 1930; to

It is hereby certified that error appears in the printed specification of the above numbered patent re uiring correction as follows: Page 2, ]jne 115, for the misspelledword sulfionid' rea sulfin'ic; page 4, lines 75 to 85, strike out the formula and insert instead nooOso Qcoon N NE;

and that the said Letters Patent should be read tvith these corrections therein that a the salme In? eonform to the record of the case in the Patent Offiee.

sled this 2dday of September, AID 1930.

{email I M. J. MOORE,

Acting Commissioner of Patents. 

